CN103880197A - Non-phosphorus environment-friendly corrosion and scale inhibitor used for landfill leachate and industrial circulating water treatment - Google Patents
Non-phosphorus environment-friendly corrosion and scale inhibitor used for landfill leachate and industrial circulating water treatment Download PDFInfo
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Abstract
The invention belongs to the field of chemical agents and specifically relates to a non-phosphorus environment-friendly corrosion and scale inhibitor used for landfill leachate and industrial circulating water treatment. The non-phosphorus environment-friendly corrosion and scale inhibitor is characterized by consisting of the following components in percent by weight: 0-15% of zinc salts, 0.5%-4.0% of imidazoles, 0-35% of acrylic multipolymers, 20%-45% of modified polycarboxylic acid, and 20%-50% of auxiliaries, wherein the acrylic multipolymers are formed through copolymerization of four monomers of acrylic acid, acrylate, 2-acrylamide-2-methyl propanesulfonic acid and propylene acetamide; the modified polycarboxylic acid is formed by mixing modified derivatives of polymaleic acid, polyepoxysuccinic acid, and polyaspartic acid; the auxiliaries are formed by compounding sulfuric acid, deionized water and a solvent. The non-phosphorus environment-friendly corrosion and scale inhibitor disclosed by the invention is specially used for treating landfill leachate in a dish tube type reverse osmosis device, also can be used for treating industrial circulating water; the formula does not contain heavy metals, orthophosphate and organic phosphonate, so that corrosion inhibition and scale inhibition are excellent; the non-phosphorus environment-friendly corrosion and scale inhibitor belongs to the environment-friendly corrosion and scale inhibitor, and has the best biological degradable performance.
Description
technical field:
The invention belongs to chemical industry medicament field, relate to specifically a kind of non-phosphate environment-friendly type inhibition anti-sludging agent of processing percolate in disc tube reverse osmosis (dt-ro) device that is specifically designed to, simultaneously also for the non-phosphate environment-friendly type inhibition anti-sludging agent of industrial cycle water treatment.
background technology:
Percolate be rubbish stack and landfill process in due to the biochemical degradation such as compacting, fermentation, the liquid of a kind of high density organic or inorganic composition that the while produces under the seepage effect of precipitation and underground water, is also named and oozes drop liquid.Percolate water quality complexity, contains multiple poisonous and hazardous inorganics and organism.Wherein organic pollutant has 99 kinds more than through technology for detection, also has 22 kinds of priority control lists that have been put into China and American National Environmental Protection Administration, and one can be directly carcinogenic, and five kinds can be brought out carcinogenic.In addition in percolate, also contain non-chlorination aromatics, chlorination aromatic series compounds such as being difficult to biodegradable naphthalene, phenanthrene, phosphoric acid vinegar, phenolic compound and amino benzenes compounds etc.Calculate with its pollution load, one ton of percolate is equivalent to 100 ~ 200 tons of municipal effluents to the harm of environment.Because current many regional domestic refuses are mixed collections, be subject to living condition, living habit, the impact in area and season, the composition of percolate is very complicated, for example there is chemical oxygen demand COD that data show life in China percolate from garbage filling field between 3000 ~ 5000mg/L, ss suspended solid is in 2000mg/L left and right, ammonia nitrogen is between 1000 ~ 3000mg/L, pH value is between 4 ~ 9, add halogenated aryl hydrocarbon, the pollutions such as heavy metal and virus, if do not processed, directly discharge will be to underground and surface water body around, soil and ecotope bring immeasurable pollution and harm, to periphery resident's healthy generation serious threat.In addition, percolate water quality is subject to the impact of many factors, such as component of refuse, quantity of precipitation, landfill yard structure, landfill time etc.Percolate in different refuse landfills, the scope of COD between several thousand to several ten thousand, BOD
5scope at hundreds of between several thousand, other indexs such as SS change also very greatly.Generally speaking, in percolate inorganics component content much larger than organic matter component content, and along with the continuity of landfill phase constantly change, organism is further degraded, BOD
5/ COD value reduces, and is unsuitable for gradually biological degradation, and after Closure of landfill site, also can continue to produce percolate 10 ~ 30 years.
The treatment process of percolate has: 1. traditional biochemical processing, and the processing of this technique functions originates from life sewage, the sewage high to this toxicity of percolate, change of water quality is large is extremely inadaptable; 2. physical and chemical process treatment technology is the new technology that in succession occurs again in recent years treating refuse percolate; 3. the reverse osmosis unit of membrane process craft is mainly for the water purification again of seawater, water purification and the water treatment device of researching and developing.The intractability of percolate is very large, and conventional treatment process is difficult to its processing to reach the emission standard of current national regulation, even external technology can meet the also very few of first grade discharging requirement.At present, adopt the method for disc tube reverse osmosis (dt-ro) system DTRO treating refuse percolate to be widely used, this system can be held back the most pollution substances in percolate, it is the principle of utilizing reverse osmosis technology, make the water molecules in percolate see through reverse osmosis membrane by pressure, most pollution substances are comprised to small molecules solute, as ammonia nitrogen etc. is greater than molecule and the ion rejection of 1nm, thereby reach the object that purifies percolate.Its operating pressure of disc tube reverse osmosis (dt-ro) device in relevant refuse leachate processing is at 6 MPa ~ 12MPa, and for its corrosion inhibiting ability wretched insufficiency of Scale inhibitors of this system, bring the metal parts part of the equipment of these high-voltage operations to have potential corrosion tendency, correlative study data show: in the pipeline of a set of refuse leachate reverse osmosis treatment device moving, be incorporated to the special detection bypass of a path built-in stainless steel lacing film, after one month, take out stainless steel lacing film and calculate its annual corrosion rate and reach 0.0084mm/a.Therefore,, along with the requirement of sewage drainage standard and supervision is more and more stricter, more terminal client, also requires more eco-friendly Water Treatment Chemicals.
The preparation of corrosion inhibiting and descaling agent and use are the effective means of controlling incrustation scale formation in process water and wastewater treatment and preventing metallic corrosion.At present, in water scale control treatments, adding scale inhibitor by chemical scale inhibition method is the most frequently used method.The main purpose of industrial cycle water treatment is inhibition, scale inhibition, kills livestock and anti-foundry loam, solves all problems but be conventionally difficult to a kind of medicament of employing, needs entirety to treat, and therefore needs to make compound prescription, in the hope of best effect.Traditional industrial circulating water anti-incrustation corrosion inhibitor generally all adopts organic phosphoric acid, or organic phosphonate and zinc salt and dispersion agent is composite forms, along with country is more and more stricter to industrial wastewater discharge requirement, in waste water, phosphorous Eutrophication materials causes the impact of environment is more and more drawn attention.The enterprise that is engaged in water treatment agent research and development both at home and abroad and produce is all at research and development high-performance non-phosphorus scale and corrosion inhibitor: as silicon series prescription, large owing to adding pharmaceutical quantities, and scale inhibition and dispersion performance is poor, is progressively eliminated; Molybdenum system (tungsten) formulation cost is too high and be difficult to come into the market, and poly-epoxy succinic acid, poly aspartic acid all belong to environmental type novel dispersant, are just progressively applied at present.As disclosed a kind of non-phosphorus scale and corrosion inhibitor of domestic patent CN 102079584 A and its preparation method and application, this non-phosphorus scale and corrosion inhibitor is made up of the component of following weight proportioning: 30 ~ 50 parts of dispersing scale inhibitors, 8 ~ 25 parts of inhibiter, 28 ~ 43 parts of auxiliary agents; Wherein, dispersing scale inhibitor is vinylformic acid-acrylic ester ternary polymkeric substance, or is that at least one and vinylformic acid-acrylic ester ternary mixed with polymers in hydrolytic polymaleic anhydride, poly aspartic acid, sodium polystyrene sulfonate used; Inhibiter is: soluble zinc salt (as zinc sulfate, zinc chloride) and phenylpropyl alcohol triazole (or methyl phenylpropyl alcohol triazole).This non-phosphorus scale and corrosion inhibitor has good Scale inhibitors corrosion inhibition, meet and be better than the requirement of " industrial circulating water treatment of cooling water design specifications " GB50050-2007, be applicable to the use of the circulating water systems such as chemical industry (large chemical fertilizer, large methyl alcohol etc.), petrochemical industry (oil refining, ethene etc.), metallurgy, electric power.But the corrosion inhibiting and descaling agent that is specifically designed to refuse leachate processing in disc tube reverse osmosis (dt-ro) device is rarely found, be necessary to develop a kind of new environmental protection medicament, without phosphorus, without nitrogen, biodegradable green circulatory water medicament, can be specifically designed to the non-phosphate environment-friendly type inhibition anti-sludging agent of processing percolate in disc tube reverse osmosis (dt-ro) device, also can be applicable in industrial cycle water treatment simultaneously.
summary of the invention:
The object of this invention is to provide a kind of non-phosphate environment-friendly type inhibition anti-sludging agent of processing percolate in disc tube reverse osmosis (dt-ro) device that is specifically designed to, also can be used for the non-phosphate environment-friendly type inhibition anti-sludging agent of industrial cycle water treatment simultaneously, environmental protection, excellent performance, have biological best degradability.
The technical solution used in the present invention is: a kind of non-phosphate environment-friendly type inhibition anti-sludging agent for percolate and industrial cycle water treatment, component by following weight per-cent forms: zinc salt 0 ~ 15%, azole 0.5 ~ 4.0%, acrylic-multipolymer (BW-810) 0 ~ 35%, modified polycarboxylic acid (BW-499) 20 ~ 45%, auxiliary agent 20 ~ 50%.
Wherein, acrylic-multipolymer (BW-810) is to be carried out copolymerization and formed by vinylformic acid (AA), acrylate, 2-acrylamide-2-methyl propane sulfonic acid (AMPS), 4 kinds of monomers of propylene ethanamide (AM);
Modified polycarboxylic acid (BW-499) is to be mixed by the modification derivant of polymaleic acid, the acid of poly-epoxy tiger amber, poly aspartic acid;
Auxiliary agent is by sulfuric acid, deionized water, composite the forming of solvent (alcohols).
Preferably, the above-mentioned non-phosphate environment-friendly type inhibition anti-sludging agent for percolate processing, is made up of the component of following weight per-cent: zinc salt 0 ~ 5%, azole 0.5 ~ 2.5%, acrylic-multipolymer (BW-810) 5 ~ 30%, modified polycarboxylic acid (BW-499) 20 ~ 45%, auxiliary agent 30 ~ 50%.
Preferably, the above-mentioned non-phosphate environment-friendly type inhibition anti-sludging agent for industrial cycle water treatment, is made up of the component of following weight per-cent: zinc salt 5 ~ 15%, azole 0.5 ~ 4.0%, acrylic-multipolymer (BW-810) 10 ~ 30%, modified polycarboxylic acid (BW-499) 20 ~ 45%, auxiliary agent 30 ~ 50%.
The preparation method of above-mentioned non-phosphate environment-friendly type inhibition anti-sludging agent is as follows:
In reactor, add zinc salt, sulfuric acid, deionized water, after being stirred well to zinc salt and dissolving completely, add successively acrylic-multipolymer (BW-810), modified polycarboxylic acid (BW-499), after stirring, add azole and solvent (alcohols), be stirred to solution transparent, obtain non-phosphate environment-friendly type inhibition anti-sludging agent.
Beneficial effect of the present invention:
(1) in formula of the present invention containing orthophosphoric acid salt, organic phosphonate, its inhibition, scale-inhibiting properties be good, can reach organic phosphine formula level completely, its scale-inhibiting properties has exceeded organic phosphine formula even; Recirculated water discharge of wastewater can reach national composite wastewater first discharge standard be phosphorus in P≤0.5mg/L, belong to environment-friendly type anti-incrustation corrosion inhibitor.
(2) in the present invention's formula, do not contain heavy metal, all easily degradeds of all monomers in formula, degraded product is CO
2, H
2o, N
2deng, all environmentally friendly; Formulation product after formulation optimization is adopted to OECD-301A testing method, be greater than 75% through the biological degradation rate of 28 days these formulation products.
(3) the not facile hydrolysis of monomer in this formula, the effective drug duration of product is longer than organic phosphine formula, and therefore, medicament is longer in the circulating water system residence time, is applicable to operation (N:5～9 times) under system high concentration multiple condition.
(4) formulation product of the present invention is for the pipeline of refuse leachate reverse osmosis treatment device, and the annual corrosion rate of stainless steel lacing film is in 0.003mm/a; The industrial application of this formulation product and testing laboratory's rotary hanging plate corrosion test effect excellence, the annual corrosion rate of carbon steel lacing film is less than 0.03mm/a.
(5) formulation product of the present invention is for industrial cycle water treatment, and in recirculated water, microorganism is more easy to control, and because medicament is not containing phosphine element, bacterium is difficult for breeding, and therefore the consumption of sterilant can reduce.
(6) in the industrial application of this formulation product, can remove from and use phosphorous higher prefilming agent, the concentration that adds that directly improves this product can be at service water pipeline formation protective membrane.
embodiment:
Below in conjunction with specific embodiment, non-phosphate environment-friendly type inhibition anti-sludging agent of the present invention and effect are described further.
Mensuration, the test method of following examples are respectively:
● calcium carbonate scale-inhibiting properties measuring method: adopt standard GB/T/T 16632-2008 " the mensuration tosca method of water conditioner scale-inhibiting properties "
● corrosion inhibition measuring method: adopt standard GB/T/T 18175-2000 " the mensuration rotary hanging plate method of water conditioner corrosion inhibition "
● disc tube reverse osmosis (dt-ro) system water quality analytical procedure: adopt standard GB/T/T 18920-2002 " urban sewage reutilization city miscellaneous water water quality "
One, preparation non-phosphate environment-friendly type inhibition anti-sludging agent
Embodiment 1
Prepare by weight percentage each component:
Azole 2%
Acrylic-multipolymer (BW-810) 10%
Modified polycarboxylic acid (BW-499) 40%
Auxiliary agent 48%
In reactor, add zinc salt, sulfuric acid, deionized water, after being stirred well to zinc salt and dissolving completely, add successively acrylic-multipolymer (BW-810), modified polycarboxylic acid (BW-499), after stirring, add azole and solvent (alcohols), be stirred to solution transparent, obtain non-phosphate environment-friendly type inhibition anti-sludging agent.This non-phosphate environment-friendly type inhibition anti-sludging agent is for the processing of certain factory's disc tube reverse osmosis (dt-ro) device percolate.
Embodiment 2
Prepare by weight percentage each component:
Zinc salt 5%
Azole 1%
Acrylic-multipolymer (BW-810) 20%
Modified polycarboxylic acid (BW-499) 25%
Auxiliary agent 49%.
The preparation method of this non-phosphate environment-friendly type inhibition anti-sludging agent is with embodiment 1.This non-phosphate environment-friendly type inhibition anti-sludging agent is for the processing of certain factory industry cooling circulating water.
Embodiment 3
Prepare by weight percentage each component:
Zinc salt 12%
Azole 3%
Acrylic-multipolymer (BW-810) 15%
Modified polycarboxylic acid (BW-499) 35%
Auxiliary agent 35%
The preparation method of this non-phosphate environment-friendly type inhibition anti-sludging agent is with embodiment 1.This non-phosphate environment-friendly type inhibition anti-sludging agent is for the processing of certain factory industry cooling circulating water.
Two, scale inhibition, corrosion inhibition are measured (static test)
1, scale-inhibiting properties is measured
At calcium hardness 750 mg/L(in calcium carbonate) and total alkalinity 350 mg/L(in calcium carbonate) condition of water quality under, add anti-incrustation corrosion inhibitor, measure the scale inhibition performance of different concns medicament, test result is in table 1.
Table 1
2, corrosion inhibition is measured
Condition of water quality and static test condition are in table 2, and test result is in table 3.
Table 2
Table 3
In standard GB/T 50050-2007 " Code for design of industrial recirculating cooling water treatment ", to the requirement of combinational antisludging agent inhibiter be: at open type system medium carbon steel corrosion rate≤0.075mm/a, the corrosion rate≤0.005mm/a of stainless steel and copper; At closed system equipment medium carbon steel corrosion rate≤0.075mm/a, the corrosion rate≤0.005mm/a of stainless steel and copper, the requirement that is up to state standards completely of above test-results.
Above-mentioned experimental result demonstration, the present invention is 4 ~ 10mg/L for the treatment of the concentration that adds of the non-phosphorus scale and corrosion inhibitor of percolate in disc tube reverse osmosis (dt-ro) device, Corrosion of Stainless Steel rate is 0 ~ 0.003mm/a.The concentration that adds for the treatment of the non-phosphate environment-friendly type inhibition anti-sludging agent of industrial circulating water is 60 ~ 100mg/L, use this medicament, corrosion of carbon steel rate is less than 0.03mm/a, Corrosion of Stainless Steel rate is that 0 ~ 0.003mm/a, brass corrosion rate are 0 ~ 0.003mm/a, is all better than the requirement of national standard " Code for design of industrial recirculating cooling water treatment " GB50050-2007.
Example 1
Shanghai destructor plant adopts the water-quality guideline of processing the percolate in disc tube reverse osmosis (dt-ro) device as following table 4:
Table 4
What this destructor plant refuse leachate was processed employing is disc tube reverse osmosis (dt-ro) device, its operating pressure is at 12MPa, and conventional its corrosion inhibiting ability wretched insufficiency of Scale inhibitors for this system has brought the metal parts part of the equipment of these high-voltage operations to have potential corrosion tendency.Data shows: therein in the pipeline of a set of refuse leachate reverse osmosis treatment device moving, be incorporated to the special detection bypass of a path built-in stainless steel lacing film, add conventional Scale inhibitors, after one month, take out stainless steel lacing film and calculate its annual corrosion rate and reach 0.0084mm/a.The non-phosphate environment-friendly type inhibition anti-sludging agent that adds the present invention research and development, adding of agent concentration is 9 mg/l, takes out stainless steel lacing film and calculate its annual corrosion rate and reach 0.0012mm/a after one month.Because the metal parts part of the equipment of these high-voltage operations is all stainless material, so there is no extension charcoal steel lacing film useless in the test of carbon steel material corrosion rate.
Example 2
Ningxia chemical company, for the treatment of recirculated cooling water in chemical plant installations, adds non-phosphorus scale and corrosion inhibitor of the present invention (preparing by embodiment 2).The said firm's recirculating cooling water system quantity of circulating water: 10000m
3, possess the water yield: 5000 m
3, amount of makeup water: 180 ~ 200 m
3/ h, design temperature: 30 ~ 38 ℃, cycles of concentration: 5 times, equipment material: carbon steel, stainless steel.To lacing film (test piece is 2 of carbon steels, 1 of stainless steel) in this recirculating cooling water system monitoring piece suspension device, the powder performance of examination non-phosphorus scale and corrosion inhibitor of the present invention, test piece test result data after one month shows: carbon steel lacing film average corrosion rate is 0.0252mm/a, stainless steel lacing film corrosion rate is 0.0008 mm/a, and corrosion rate is low.
Claims (4)
1. the non-phosphate environment-friendly type inhibition anti-sludging agent for percolate and industrial cycle water treatment, it is characterized in that: the component by following weight per-cent forms: zinc salt 0 ~ 15%, azole 0.5 ~ 4.0%, acrylic-multipolymer 0 ~ 35%, modified polycarboxylic acid 20 ~ 45%, auxiliary agent 20 ~ 50%; Wherein, acrylic-multipolymer is to be carried out copolymerization and formed by vinylformic acid, acrylate, 2-acrylamide-2-methyl propane sulfonic acid, 4 kinds of monomers of propylene ethanamide; Modified polycarboxylic acid is to be mixed by the modification derivant of polymaleic acid, the acid of poly-epoxy tiger amber, poly aspartic acid; Auxiliary agent be by sulfuric acid, deionized water, alcoholic solvent is composite forms.
2. a kind of non-phosphate environment-friendly type inhibition anti-sludging agent for percolate and industrial cycle water treatment according to claim 1, it is characterized in that: the component by following preferred weight percent forms: zinc salt 0 ~ 5%, azole 0.5 ~ 2.5%, acrylic-multipolymer 5 ~ 30%, modified polycarboxylic acid 20 ~ 45%, auxiliary agent 30 ~ 50%.
3. a kind of non-phosphate environment-friendly type inhibition anti-sludging agent for percolate and industrial cycle water treatment according to claim 1, it is characterized in that: the component by following preferred weight percent forms: zinc salt 5 ~ 15%, azole 0.5 ~ 4.0%, acrylic-multipolymer 10 ~ 30%, modified polycarboxylic acid 20 ~ 45%, auxiliary agent 30 ~ 50%.
4. the preparation method of the non-phosphate environment-friendly type inhibition anti-sludging agent for percolate and industrial cycle water treatment described in claim 1 ~ 3, it is characterized in that: step is as follows: in reactor, add zinc salt, sulfuric acid, deionized water, after being stirred well to zinc salt and dissolving completely, add successively acrylic-multipolymer, modified polycarboxylic acid, after stirring, add azole and solvent alcohols, be stirred to solution transparent, obtain non-phosphate environment-friendly type inhibition anti-sludging agent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143675A (en) * | 2018-12-11 | 2019-08-20 | 德蓝水技术股份有限公司 | Industrial circulating cooling water system without phosphorus prefilming agent and preparation method thereof |
| CN112499779A (en) * | 2020-11-26 | 2021-03-16 | 山东天庆科技发展有限公司 | Low-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN112978945A (en) * | 2020-12-31 | 2021-06-18 | 湖南伟方环保技术股份有限公司 | Special scale inhibitor for papermaking black liquor and preparation method thereof |
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| JP2001137892A (en) * | 1999-11-11 | 2001-05-22 | Japan Organo Co Ltd | Water treating chemical |
| CN102079584A (en) * | 2010-12-14 | 2011-06-01 | 成都齐达水处理工程股份有限公司 | Non-phosphorus scale and corrosion inhibitor, and preparation method and applications thereof |
| CN103319007A (en) * | 2012-03-21 | 2013-09-25 | 中国石油化工股份有限公司 | Method for reuse of reclaimed water in circulating cooling water |
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2014
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Patent Citations (4)
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| JPS6099396A (en) * | 1983-11-04 | 1985-06-03 | Kurita Water Ind Ltd | Obstruction preventive agent of water system |
| JP2001137892A (en) * | 1999-11-11 | 2001-05-22 | Japan Organo Co Ltd | Water treating chemical |
| CN102079584A (en) * | 2010-12-14 | 2011-06-01 | 成都齐达水处理工程股份有限公司 | Non-phosphorus scale and corrosion inhibitor, and preparation method and applications thereof |
| CN103319007A (en) * | 2012-03-21 | 2013-09-25 | 中国石油化工股份有限公司 | Method for reuse of reclaimed water in circulating cooling water |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110143675A (en) * | 2018-12-11 | 2019-08-20 | 德蓝水技术股份有限公司 | Industrial circulating cooling water system without phosphorus prefilming agent and preparation method thereof |
| CN110143675B (en) * | 2018-12-11 | 2021-11-19 | 德蓝水技术股份有限公司 | Phosphorus-free pre-filming agent for industrial circulating cooling water system and preparation method thereof |
| CN112499779A (en) * | 2020-11-26 | 2021-03-16 | 山东天庆科技发展有限公司 | Low-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN112978945A (en) * | 2020-12-31 | 2021-06-18 | 湖南伟方环保技术股份有限公司 | Special scale inhibitor for papermaking black liquor and preparation method thereof |
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